Ethers of partially esterified alkylolamines



Patented Jan. i4, 1941 v 2 9 9 UNITED STATES @PATENT OFFICE a'rnsns or PARTIALLY nsralurmn Melvin De Groote, University City, and Bernhard Keiser and Charles M. Blair, Jr., Webster Groves, Mo., assignors, by mesne assignments,

to Petrolite Corporation, Ltd., a corporation of Delaware v Serial No. 208,220 14 Claims. (Cl. 260-404). V

This invention relates to new products adaptpassed through the reaction mixture to cause ed for use. as wetting, dispersing or emulsifying the reaction to proceed more rapidly. agents. It relates more particularly to new The partially esterified alkylolamines used for ethereal condensation products ofpartlally esterthe preparation of the new products of e present invention may be prepared in vario ways.

In general, they may be represented by t e formula:

No Drawing. Application May 16, 1938,

oducts "of.

products, the ethereal conde p ,m partially esterified alkylolamines with glycerin have important advantages. The invention in- 10 eludes not only these new products, but also a new process for their preparation. The new i which R1 d 3 are alkyl ps 8 hereproducts are quite stable and are highly effective "in defined, Substituted a l p W ch may in acicl solution. be the same or different, at least one oiwhich 15 The new products of the present invention h x least n R4 s i n 4 p emay be represented by the formula: senting methyl or the carbon-linked chain of a X 1 fatty acid) and at least one of which has at least one OH (alcoholic hydroxyl) substituent,.compounds having an RQCOO substituent, and an OH x substituent in the same substituted kyl group,

in which R represents an alkyl, aralkyl- 6 am with-theother alkyl groups substituted or unsubcyclic group and in which the X's represent alsummed being inchided' L i I kyl, aralkyl, alicyclic, alkylol, hydroxyalicycllc, ar- In f 'f ff g and the appended claims, alkylol or esterined alkylol, aralkylol or hydroxyh term fatty acld 15 designate alicyclic groups, alike or dliferent, and Z is the iy carboxylic acids of the aliphatic series, lncludresidue of va. polyhydric alcohol. The radicals mg both unsaturated. and Saturated acids as well represented by x may be mdm-erenfly selected, as the substituted acids which may occur in natexcept that at least one must contain an RCoo ural fats or oils, such as ricinoleic acid, and modisubstitutent (R4 representing methyl or the carficat1n of the w whlch occur in natural bon linked chain of a tatty acid oils, such as those 1n blown or bodied oils; and 30 These new products are advantageously the term higher fatty acid is usedto desigduced by reaction between the corresponding nate those carboxylic acids, generally having at alkylolamme and polyhydflc alcohol, in accord least 8 carbon atoms, which occur combined with glycerin in natural oils and fats; It is underancexwith the equation' x stood that the terms alkylol and alkyl" are 85 used conventionally in chemistry to refer to parv NR0H+HOZ R0-Z+H,0 amn compounds which are non-cyclic and all-- phatic in nature. We have found, however, that the alicyclic and hydroxyallcyclic, as well a the 40 'x g fi g g gmg gg 23 g? gg g g ggg aralkyl and aralkylolamines are, with espect to polyhydrlc alcohol with formation 01' an ether. the reaction involved in the variQus phases of This reaction may be caused to take place by the present mventmn' snfmar f l heating the constituents togetherto a temperamg alkyl and alkyml ammesl W thevumitationr ture excess C advantageously above that the aralkyl and aralkylol compounds have 150 C. but below the point of decomposition or the hnkage t0 the nitrPgen in the side 45 volatilization of the constituents, for a r'elaf this n; for h P rp se of detively long period of. time, for example, one or crlbm the present inven i n n y. it i undertwo days, with reflux, if desired, to prevent undue stood that the terms alkyl and alkylol in- I volatilization of relatively volatile compounds. A elude wi h n their scope alicycllc. r k l, hy-, current of inert gas, such as dry nitrogen, may be droxyalicyclic and aralkylol grou 5o One advantageous method of preparing the partially esterlfied alkylolamines is that described in our application Serial No. 180,993, filed December 21, 1937, by reaction between a triglyceride of a fatty acid, or other ester of a fatty acid, and an alkylolamine having more than one alcoholichydroxyl, the proportions of the ester and the alkylolamine being such that after replacement of the glycerin or other alcohol of the fatty acid ester used, there will be at least one free alcoholic hydroxyl in the esterlfied alkylolamine. esterified hydroxyl group and at least one free hydroxyl group, are herein referred to as partially esterlfied alkylolamines. The free alcoholic hydroxyl of the partially esterlfied amine is available for condensation with a corresponding hydroxyl group of a polyhydric alcohol in accordance with the present invention. However, the preparation of the partially esterlfied alkylolamines which may be used is not limited to the procedure described in said prior application, as they may also be prepared by suitable reaction between an acyl halide, such as acyl chloride, and a tertiary alkylolamine, or in other ways. Also, it is to be understood that the alkylolamines used in accordance with the present invention need not be esters of tertiary alkylolamines with the higher fatty acids, but include tertiary alkylolamines partially esterlfied with the lower fatty acids, such as acetic acid, propionic acid, butyric acid, etc.

Similarly, various polyhydric alcohols, including, ethylene glycol, propylene glycol, glycerin, polyglycerols, polyglycols, etc., may be used in the preparation of the new ethers. The products obtained by the condensation of partially esterifled alkylolamines with glycerin have important advantages, and are the preferred compounds. i

If the reaction described in our prior application Serial No. 180,993 is carried out for the production of the partially esterlfied alkylolamines, the alcoholysis which takes place will result in the formation of a partially esterified alkylolamine, with liberation of glycerin and formation of a reaction mixture suitable for the production of new ethers of the present invention. When using such a product, it is advantageous to add more glycerin, after the substantial completion' of the alcoholysis and formation of the partially esterlfied alkylolamine and liberation of glycerin, to promote the reaction involved in the production of the new ethers, and to provide either equimolecular proportions of amine and glycerin, or an excess of glycerin.

Among the amines which may be partially esterlfied for use in the production of the new products of the present invention are a wide rangeof tertiary alky'lol and tertiary alkyl alkylolamines. The two essentials are that the alkylolamine contain at least two alcoholic hydroxyl groups, which may be attached to the same or different carbon chains, and be a tertiary amine, that is, with three alkyl or alkylol groups linked through carbon atoms to the nitrogen atom. Included among the suitable amines are triethanolamine, diethanolalkylamines, such as diethanolethylamine, diethanolpropylamine, etc., tertiary glyceryl amines, such as tri-dihydroxypropylamine, dihydroxypropyldialkylamines, such as dihydroxypropyldiethylamine, tripropanolamine, dipropanolmethylamine, cyclohexanoldiethanolamine, di-cyclohexanolethylamine, etc. All such products may be readily prepared by known processes, and all of them are tertiary amines hav- Such alkylolamines, having at least one- 'ing at least two alcoholic hydroxyl groups, thus being adapted to form esterswith higher fatty acids, such esters having at least one free bydroxyl group. Typical of the amines which may be used are the following:

(C2H4OID3N Triethanolamlne (CZHE) Diethanolethylaminc CH: Diethanolmethylamine 2Hs(0H)!]aN Trl-dlhydroxypropylamine (triglyoerylamine) [C:Ht(OH)2] [C:H:(OH)z]N 2 5) Di-dihydroxypropylethyiamine (diglycerylethylamine) HHKOHM (C2H5)N 2 6) Dihydroxypropyldicthylamine (glyceryl diethylamine) (CsHaH)aN Tripropanolamine (CaHoOH) (C3HOOH)N z s) I Dipropanoletliylamine [C3H5(CH5)OH] [CaH(CaH5) OH]N 2 5) Di-phenylpropanoletbylamine (CzH4OH) (c2H4OH)f N aHioOH) Cyclohexanoldietbanolaxnine oHw H) (CtH oOH)-N (C2Hs) Dicyclohexanolethylamine (CAHBOH)JN Tributanolamine (ClHtOH) (C4HaOH)-N (CzHrOH) Dibutanoletbanolamine 011, soya bean oil, sunflower seed oil, linseed oil,

Perilla oil, etc., as well as animal and marine and blown castor oil have somewhat special char acteristics due to the presence of oxygen in the long hydrocarbon chain characteristic of such fatty acids.

If glycerin, or other polyhydric alcohol having more than two free hydroxyl groups, or a' partialcourse of the reaction, as by the condensation of one molecule of the partially esterified alkylolamine having more than one free hydroxyl group with two molecules of the polyhydric alcohol, or by the condensation of one molecule of the polyhydric alcohol with two or more molecules of the partially esterified alkylolamine. In any case, the resulting condensation products are ethereal derivatives of the initial starting material. I

The invention will be further illustrated by the following specific examples, although it is not limited thereto.

Example 1.--Commercial triethanolamine and cocoanut oil, in the proportions of 1 mole of cocoanut oil to 3 moles of triethanolamine are heated to. a temperature between about 160 C. and 180 C. for about two hours. The resulting product consists mainly of the mono-fatty acid ester of triethanolamine, with minor proportions of the di-fatty acid ester, the tri-fatty acid ester, glycerin, etc. To this reaction product is added somewhat more than 2 moles of glycerin,

' and the resulting mixture is heated to a temperature between about 160 C. and 180 C. for about two days. If desired, a current of dry nitrogen or other inert gas may be passed through to speed up the reaction. Condensation occurs between the fatty acid ester of the triethanolamine, and the glycerin, with the production of ethereal reaction products, such as the dihydroxypropyl ether of the mono-fatty acid ester of triethanolamine and other more complex ethereal reaction products.

The final product has-extremely good wetting, emulsifying and detergent properties and is highly effective in acid solution.

resulting mixture is further heated for a period of about two days, with condensation between the glycerin .and the di-ricinoleic acid ester of the triglycerylamine, and the production of corresponding ethereal condensation products.

Example 3.--Blown rapeseed oil'and diethanolethylamine, in the molecular proportions of '3 moles of the amine to 1 mole of the oil are heated together to a temperature between about 150 C.

and 180 C. for about two hours, with the production of a reaction product containing a large proportion of the mono-ester of the diethanolethylamine, together with unreacted starting materiai, glycerin, etc. Something in excess of two moles of glycerin are added to the reaction mixture, and the resulting product is heated to about 150 C. to 180 C. for about two days, with the production of ethereal reaction products of glycerin and the mono-ester of the diethanolethylamine. r

The foregoing examples illustrate the production of certain of the new products of the present invention. In place of the partially esterified tertiary alkylolamines of the examples, any other available tertiary alkylolamine having at least one esterified hydroxyl group and at least'one free hydroxyl group, such as the products obtained by the partial esterification of thepolyhydroxyalkylolamines previously referred to may be used; while in place of the glycerin of the examples, other polyhydric alcohols, such as ethylene glycol, propylene glycol, etc., may be used. In general, ethers derived from'glycerin and the partially esterified tertiary alkylolamines, particularly the monoand di-fatty'acid esters of triethanolamine, have important advantages as wetting, dispersing and emulsifying agents. a

We claim:

1. Ethers of partially esterified tertiary alkylclamines with polyhydric alcohols.

-2. Ethers of partially esterified tertiary alkylolamines with glycerin.

3. Ethers of partially esterified triethanolamines with polyhydric alcohols.

4. Ethers of partially esterified triethanolamines with glycerin.

5. Ethers'of mono-fatty acid esters of tertiary alkylolamines having more than one hydroxy group with polyhydric alcohols.

6. Ethers of mono-higher fatty acid esters of tertiary alkylolamines having more than one hydroxy group with polyhydric alcohols.

7. Ethers of mono-fatty acid esters of trtethanolamine with polyhydric alcohols.

8. Ethers of mono-fatty acid esters of triethanolamine with glycerin.

9. Ethers of mono-higher fatty acid esters of triethanolamine with glycerin.

10. Reaction products ofpartially esterified tertiary alkylolamines and polyhydric alcohols,

said reaction products having an ether linkage.

11. Reaction products of compounds of the class consisting of monoand di-fatty acid esters of triethanolamine and glycerin, said reaction products having an ether linkage.

12. The process of preparing wetting, emulsifying and dispersing agents, which comprises heating a partially esterifled tertiary alkylolamine with a polyhydric alcohol to a. temperature in excess of C. for a period of time sufiicient'to cause condensation with elimination of water and the production of a reaction product having an ether linkage.

13. The process as in the preceding claim in which a current of inert gas is passed through the reaction mixture.

14. The process as in claim 12 when carried out at a temperature between about "C. and C.

MELVIN- DE GRooTE. BER-NI-IARD K'EISER. cnAR Es M. BLAIR; JR. 

